U.S. patent application number 13/201316 was filed with the patent office on 2011-12-08 for coating method and coated article.
This patent application is currently assigned to MITSUBISHI ELECTRIC CORPORATION. Invention is credited to Teruhiko Kumada, Reiji Morioka, Yoshinori Yamamoto, Yasuhiro Yoshida.
Application Number | 20110300370 13/201316 |
Document ID | / |
Family ID | 42561769 |
Filed Date | 2011-12-08 |
United States Patent
Application |
20110300370 |
Kind Code |
A1 |
Yoshida; Yasuhiro ; et
al. |
December 8, 2011 |
COATING METHOD AND COATED ARTICLE
Abstract
Provided is a coating method, including the steps of: applying a
coating composition including inorganic fine particles and
fluororesin particles in an aqueous medium onto a material to be
coated; drying the coating composition on the material to be coated
to remove the aqueous medium, thereby forming a porous film formed
of the inorganic fine particles, the porous film having the
fluororesin particles therein and having voids; and applying one or
more water-soluble substances selected from the group consisting of
a water-soluble surfactant and a water-soluble polymer onto the
porous film, thereby filling the one or more water-soluble
substances in the voids of the porous film. According to the
coating method, there can be formed a coated article having a
coating film which exhibits the excellent effect for inhibiting the
attachment of oil stains for a long period and from which, even if
oil stains are attached, the oil stains can be easily removed by
wiping or washing with water.
Inventors: |
Yoshida; Yasuhiro; (Tokyo,
JP) ; Yamamoto; Yoshinori; (Tokyo, JP) ;
Kumada; Teruhiko; (Tokyo, JP) ; Morioka; Reiji;
(Tokyo, JP) |
Assignee: |
MITSUBISHI ELECTRIC
CORPORATION
Tokyo
JP
|
Family ID: |
42561769 |
Appl. No.: |
13/201316 |
Filed: |
February 8, 2010 |
PCT Filed: |
February 8, 2010 |
PCT NO: |
PCT/JP10/51793 |
371 Date: |
August 12, 2011 |
Current U.S.
Class: |
428/320.2 ;
427/373 |
Current CPC
Class: |
B05D 1/36 20130101; B05D
2420/01 20130101; B05D 2451/00 20130101; B08B 17/06 20130101; Y10T
428/249994 20150401; B05D 2420/01 20130101; B05D 2451/00 20130101;
B05D 2401/20 20130101; B05D 2401/20 20130101; B05D 2401/20
20130101; B05D 2401/32 20130101; C09D 5/1637 20130101; B05D 5/083
20130101; C09D 5/1625 20130101 |
Class at
Publication: |
428/320.2 ;
427/373 |
International
Class: |
B32B 3/26 20060101
B32B003/26; B05D 3/02 20060101 B05D003/02 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 13, 2009 |
JP |
2009-031673 |
Claims
1. A method of coating a material, the method comprising: applying
a coating composition comprising at least one inorganic fine
particle and at least one fluororesin particle in an aqueous medium
onto a material to be coated; drying the coating composition on the
material to be coated to remove the aqueous medium, thereby forming
a porous film comprising the at least one inorganic fine particle,
the porous film comprising the at least one fluororesin particle
dispersed therein and having voids; and applying a water-soluble
polymer onto the porous film, thereby filling the voids of the
porous film with the water-soluble polymer.
2. The method of claim 1, wherein the coating composition further
comprises an antioxidant.
3. The method of claim 1, comprising applying the water-soluble
polymer and an antioxidant onto the porous film, thereby filling
the voids of the porous film with the water-soluble polymer and the
antioxidant.
4. The method of claim 1, wherein a content of the at least one
inorganic fine particle in the coating composition is 0.5 mass % to
60 mass %.
5. The method of claim 1, wherein a content of the at least one
fluororesin particle in the coating composition is 5 parts by mass
to 70 parts by mass with respect to 100 parts by mass of the at
least one inorganic fine particle.
6. A coated article, comprising a coating film which comprises a
porous film comprising at least one inorganic fine particle with at
least one fluororesin particle dispersed in the porous film, and a
water-soluble polymer filling voids of the porous film.
7. The article of claim 6, wherein the water-soluble polymer and an
antioxidant fill the voids of the porous film.
8. The article of claim 6, wherein a content of the at least one
fluororesin particle in the coating film is 5 parts by mass to 70
parts by mass with respect to 100 parts by mass of the at least one
inorganic fine particle.
9. The article of claim 6, wherein an amount of the water-soluble
polymer filling the coating film is 5 parts by mass to 120 parts by
mass with respect to 100 parts by mass of the at least one
inorganic fine particle.
10. The article of claim 7, wherein an amount of the antioxidant
filling the coating film is 0.05 part by mass to 30 parts by mass
with respect to 100 parts by mass of the at least one inorganic
fine particle.
11. The method of claim 2, wherein a content of the at least one
inorganic fine particle in the coating composition is 0.5 mass % to
60 mass %.
12. The method of claim 3, wherein a content of the at least one
inorganic fine particle in the coating composition is 0.5 mass % to
60 mass %.
13. The method of claim 2, wherein a content of the at least one
fluororesin particle in the coating composition is 5 parts by mass
to 70 parts by mass with respect to 100 parts by mass of the at
least one inorganic fine particle.
14. The method of claim 3, wherein a content of the at least one
fluororesin particle in the coating composition is 5 parts by mass
to 70 parts by mass with respect to 100 parts by mass of the at
least one inorganic fine particle.
15. The method of claim 4, wherein a content of the at least one
fluororesin particle in the coating composition is 5 parts by mass
to 70 parts by mass with respect to 100 parts by mass of the at
least one inorganic fine particle.
16. The article of claim 7, wherein a content of the at least one
fluororesin particle in the coating film is 5 parts by mass to 70
parts by mass with respect to 100 parts by mass of the at least one
inorganic fine particle.
17. The article of claim 7, wherein an amount of the water-soluble
polymer filling the coating film is 5 parts by mass to 120 parts by
mass with respect to 100 parts by mass of the at least one
inorganic fine particle.
18. The article of claim 8, wherein an amount of the water-soluble
polymer filling the coating film is 5 parts by mass to 120 parts by
mass with respect to 100 parts by mass of the at least one
inorganic fine particle.
19. The article of claim 8, wherein an amount of the antioxidant
filling the coating film is 0.05 part by mass to 30 parts by mass
with respect to 100 parts by mass of the at least one inorganic
fine particle.
20. The article of claim 9, wherein an amount of the antioxidant
filling the coating film is 0.05 part by mass to 30 parts by mass
with respect to 100 parts by mass of the at least one inorganic
fine particle.
Description
TECHNICAL FIELD
[0001] The present invention relates to a coating method and a
coated article, in particular, to a coating method for providing a
coating film which exhibits an excellent effect for inhibiting the
attachment of oil stains for a long period, and from which oil
stains can be removed by wiping or washing with water, and a coated
article coated with the coating film.
BACKGROUND ART
[0002] In kitchens, factories, and the like, oil stains occur from
oil mist and the like attaching to the surfaces of various
articles, causing articles to become unsightly and in some cases
causing sanitation problems such as bad odors. Thus, in recent
years, a wide range of developments have been made in coating
technologies for inhibiting the attachment of oil stains to the
surfaces of articles. Specifically, a method of forming a coating
film on the surface of articles by using a coating composition
prepared by blending a hydroxyl-group-containing silicone-based
additive and/or a hydroxyl-group-containing fluorine-based additive
in a powder coating material containing a polyester resin and a
blocked isocyanate (see, for example, Patent Document 1) and a
method of forming a coating film on the surface of each article by
using a coating composition prepared by blending a specific
fluorosilicone compound as a coating material modifier in a coating
material (see, for example, Patent Document 2) has been proposed.
In addition, a method of forming a coating film by applying an
undercoating material containing water glass, a hardening agent for
water glass, and an aggregate onto the surface of articles, thereby
forming an undercoating layer, and then applying a topcoating
material containing water glass and silica fine particles but not
containing a hardening agent for water glass onto the undercoating
layer, thereby forming a topcoating layer, followed by firing (see,
for example, Patent Document 3), and a method of forming a coating
film on the surface of articles by using a resin composition
containing a fluorine-based oligomer having a plurality of
predetermined water-repellent groups and hydrophilic groups in its
molecule (see, for example, Patent Document 4) have been proposed.
Further, a method of decomposing oil stains attached to the
surfaces of articles by using a photocatalyst (see, for example,
Patent Document 5) has also been proposed.
Citation List
Patent Documents
[0003] Patent Document 1: JP 09-53026 A
[0004] Patent Document 2: JP 08-60030 A Patent Document 3: JP
2006-152221 A Patent Document 4: JP 2009-127015 A Patent Document
5: JP 09-4900 A
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0005] However, although conventional coating technologies have
been able to provide an effect for inhibiting the attachment of oil
stains, until now the coating technologies have had the problem
that attached oil stains cannot be removed satisfactorily, and the
problem that the effect for inhibiting the attachment of oil stains
is difficult to maintain for a long period.
[0006] Generally, the attachment of oil stains occurs on both
hydrophobic (water-repellent) oil-repellent coating films such as
fluororesin films and hydrophilic (oil-repellent) coating films
such as hydrophilic resin films. When a hydrophobic film is used as
a coating film, oil is likely to adhere easily to the film, and
hence oil stains are more liable to attach to the film, moreover,
it is difficult to remove the attached oil stains by wiping or
washing with water. When a fluororesin film or the like is used as
a coating film, the degree of attachment of oil stains is less
compared with the case of using a general hydrophobic coating film,
but it is still difficult to remove oil stains attached to the
surfaces of articles by wiping or washing with water to the same
extent as the case where a general hydrophobic coating film is
used. On the other hand, when a hydrophilic film is used as a
coating film, oil stains may get into the minute concave portions
on the surface of the film or hydrophilic groups may chemically
react with oil, making it difficult to remove the attached oil
stains by wiping or washing with water in some cases.
[0007] Further, oil stains attached to the surfaces of articles can
be removed at the time of wiping or washing with water by using a
water based cleaning solution containing a surfactant. However,
when reaction such as oxidation progress as time passes, resulting
in the attachments of oil stains, not only washing with water but
also wiping oil stains per se often becomes difficult. Thus, it may
become necessary to clean oil stains by using alkalis, solvents, or
the like.
[0008] Although a technology for decomposing oil stains by using a
photocatalyst exhibits a good effect on the attachment of very
small amounts of oil stains, it does not provide a sufficient
effect on the attachment of large amounts of oil stains.
[0009] The present invention has been made to solve the problems
described above, and an object of the invention is to provide a
coating method capable of forming a coating film which exhibits an
excellent effect for inhibiting the attachment of oil stains for a
long period and from which, even if oil stains are attached, the
oil stains can be easily removed by wiping or washing with
water.
[0010] In addition, another object of the present invention is to
provide a coated article having a coating film which exhibits an
excellent effect for inhibiting the attachment of oil stains for a
long period and from which, even if oil stains are attached, the
oil stains can be easily removed by wiping or washing with
water.
Means for Solving the Problems
[0011] The inventors of the present invention have intensively
studied to solve the problems described above. Consequently, the
inventors have found that it is possible to provide a coating film
which exhibits an excellent effect for inhibiting the attachment of
oil stains for a long period and from which, even if oil stains are
attached, the oil stains can be easily removed by wiping or washing
with water, by filling the voids of a porous film with a
predetermined water-soluble substance formed of inorganic fine
particles with fluororesin particles dispersed therein.
[0012] That is, the present invention is a coating method,
including the steps of: applying a coating composition including
inorganic fine particles and fluororesin particles in an aqueous
medium onto a material to be coated; drying the coating composition
on the material to be coated to remove the aqueous medium, thereby
forming a porous film formed of inorganic fine particles, the
porous film having the fluororesin particles dispersed therein and
having voids; and applying one or more water-soluble substances
selected from the group consisting of a water-soluble surfactant
and a water-soluble polymer onto the porous film, thereby filling
the voids of the porous film with one or more of the water-soluble
substances.
[0013] Further, the present invention is a coated article,
including a coating film comprising a porous film formed of
inorganic fine particles with fluororesin particles dispersed in
the porous film, and one or more water-soluble substances selected
from the group consisting of a water-soluble surfactant and a
water-soluble polymer, the water-soluble substances filling the
voids of the porous film.
Effects of the Invention
[0014] According to the present invention, a coating method capable
of forming a coating film which exhibits an excellent effect for
inhibiting the attachment of oil stains for a long period and from
which, even if oil stains are attached, the oil stains can be
easily removed by wiping or washing with water can be provided.
According to the present invention, a coated article having a
coating film which exhibits an excellent effect for inhibiting the
attachment of oil stains for a long period and from which, even if
oil stains are attached, the oil stains can be easily removed by
wiping or washing with water can also be provided.
MODES FOR CARRYING OUT THE INVENTION
Embodiment 1
[0015] A coating method of the present invention includes the steps
of: applying a predetermined coating composition onto a material to
be coated; drying the coating composition on the material to be
coated, thereby forming a predetermined porous film; and applying a
predetermined water-soluble substance onto the porous film, to fill
the voids of the porous film.
[0016] The coating composition that is used in the coating method
of the present invention includes inorganic fine particles and
fluororesin particles in an aqueous medium.
[0017] The inorganic fine particles are the components for forming
the porous film. The inorganic particles are not particularly
limited as long as the inorganic particles are capable of forming a
porous film. Examples thereof include metal fine particles of
elements such as silicon, magnesium, aluminum, titanium, cerium,
tin, zinc, germanium, indium, and antimony, and fine particles of
oxides and nitrides of those elements. These fine particles may be
used on their own, or as a mixture thereof.
[0018] Further, from the viewpoint of enhancing the bonding force
between the inorganic fine particles in the porous film, it may be
possible to add, to the coating composition, a common binder such
as a sol of a metal oxide such as silica or alumina, any of the
various silicates such as sodium silicate and lithium silicate, a
metal alkylate, aluminum phosphate, or -alumina. Although, if a
binder including inorganic fine particles is used, the binder may
be used alone.
[0019] The average particle diameter of the inorganic fine
particles is not particularly limited. When the average particle
diameter is 20 nm or less, a porous film having high strength can
be formed by drying or heating even if a binder is not added. For
example, a porous film having a relatively high strength can be
formed by simply drying, at room temperature, silica fine particles
having an average particle diameter of 20 nm or less. Here, the
term "average particle diameter" herein means the average value of
particle diameter values obtained by performing particle size
distribution measurement by a laser diffraction/scattering
method.
[0020] The content of the inorganic fine particles in the coating
composition is not particularly limited and is preferably 0.5 mass
% to 60 mass %, more preferably 1 mass % to 40 mass %. Here, the
mass of the inorganic fine particles varies depending on its dried
state or the like, and hence, after the coating composition is
dried at 100.degree. C., to evaporating water sufficiently, the
mass is measured, and the resultant mass is defined as the mass of
the inorganic fine particles (hereinafter, the mass of the
inorganic fine particles has the same meaning as described above).
When the content of the inorganic fine particles is less than 0.5
mass %, the thickness of the resultant porous film becomes too
thin. Thus, the amount of water-soluble substance filling the
porous film becomes small, with the result that attached oil stains
cannot be removed sufficiently by wiping or washing with water in
some cases. On the other hand, when the content of the inorganic
fine particles is more than 60 mass %, the thickness of the
resultant porous film becomes too thick, sometimes resulting in the
occurrence of defects such as cracks in the porous film.
[0021] The fluororesin particles are the components that impart
dirt prevention properties to the porous film formed of the
inorganic fine particles. When the fluororesin particles are
contained in the coating composition, the fluororesin particles are
dispersed in the porous film formed of the inorganic fine
particles. The porous film has a surface in which the fluororesin
particles are dispersed and exposed, hence it is difficult for both
hydrophilic and hydrophobic substances to attach thereto. Thus, the
porous film can inhibit not only the attachment of oil mist causing
oil stains directly but also the attachment of dust and the like
which promotes the attachment of oil mist indirectly. Further,
because the fluororesin particles are dispersed and exposed on the
surface of the porous film, even in the case that oil stains are
attached to the porous film, the oil stains can be easily removed
at the time of wiping or washing with water, and the reattachment
of oil stains can also be inhibited. In particular, the fluororesin
particles are also components that impart lubricity to the porous
film, and hence the effectiveness of wiping oil stains can be
further improved.
[0022] The fluororesin particles are not particularly limited and
examples thereof include polytetrafluoroethylene (PTFE), a
tetrafluoroethylene-hexafluoropropylene copolymer (FEP), a
tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), a
fluorinated ethylene-vinyl ether copolymer (FEVE), an
ethylene-tetrafluoroethylene copolymer (ETFE), an
ethylene-chlorotrifluoroethylene copolymer (ECTFE), a
polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene
(PCTFE), polyvinyl fluoride (PVF), copolymers thereof, and mixtures
thereof, and particles formed from mixtures of those fluororesins
with other resins and the like.
[0023] The average particle diameter of the fluororesin particles
is not particularly limited and is preferably 0.05 .mu.m to 200
.mu.m, more preferably 0.1 .mu.m to 80 .mu.m. When the average
particle diameter of the water-insoluble polymer particles is less
than 0.05 .mu.m, the hydrophobic portion in the porous film becomes
smaller. As a result, the effect of inhibiting the attachment of
oil stains is not exerted sufficiently in some cases. On the other
hand, when the average particle diameter of the water-insoluble
polymer particles is more than 200 .mu.m, the unevenness of the
surface of the porous film becomes larger. As a result, dust,
powder dust, and the like easily attach to the surfaces, sometimes
promoting the attachment of oil stains.
[0024] The content of the fluororesin particles in the coating
composition is not particularly limited and is preferably 5 parts
by mass to 70 parts by mass, more preferably 10 parts by mass to 50
parts by mass with respect to 100 parts by mass of the inorganic
fine particles. When the content of the fluororesin particles is
less than 5 parts by mass, the effect of inhibiting the attachment
of oil stains is not exerted sufficiently in some cases. On the
other hand, when the content of the fluororesin particles is more
than 70 parts by mass, oil stains may easily attach to the coating
film. Note that because the fluororesin particles are a nonvolatile
component, the content of the fluororesin particles in the coating
composition described above is identical to the content of the
fluororesin particles in the coating film.
[0025] In order to form a porous film having fluororesin particles
dispersed therein, the fluororesin particles need to be dispersed
in the coating composition. Thus, the coating composition is
preferably produced by blending a dispersion prepared by dispersing
the fluororesin particles in water using the effect of hydrophilic
groups contained in a surfactant or the fluororesin particles. This
method of blending the dispersion in the coating composition is the
simplest method of producing the coating composition, but the
coating composition can also be produced by directly blending the
fluororesin particles into the coating composition, thereby causing
self-emulsification, or by dispersing the fluororesin particles in
the coating composition with a homogenizer or the like.
[0026] The coating composition includes an aqueous medium, in
addition to the above-mentioned inorganic fine particles and
fluororesin particles. The kind of aqueous medium is not
particularly limited and is preferably water. Alternatively, it is
also possible to use, as the aqueous medium, a mixture of water and
a polar solvent compatible with water.
[0027] The kind of water is not particularly limited. However, in
the case in which the water has a large mineral content, if the
average particle diameter of the inorganic fine particles such as
silica is small or if the concentration of the inorganic fine
particles is high, some of the inorganic fine particles may
aggregate. Thus, the use of deionized water is preferred. However,
if the inorganic fine particles do not aggregate, tap water or the
like may be used instead.
[0028] Examples of the polar solvent include: alcohols such as
ethanol, methanol, 2-propanol, and butanol; ketones such as
acetone, methyl ethyl ketone, and diacetone alcohol; esters such as
ethyl acetate, methyl acetate, cellosolve acetate, methyl lactate,
ethyl lactate, and butyl lactate; ethers such as methyl cellosolve,
cellosolve, butyl cellosolve, and dioxane; glycols such as ethylene
glycol, diethylene glycol, and propylene glycol; glycol ethers such
as diethylene glycol monomethyl ether, triethylene glycol
monomethyl ether, propylene glycol monomethyl ether, and
3-methoxy-3-methyl-1-butanol; and glycol esters such as ethylene
glycol monomethyl ether acetate, propylene glycol monomethyl ether
acetate, diethylene glycol monobutyl ether acetate, and diethylene
glycol monoethyl ether acetate.
[0029] The content of the aqueous medium in the coating composition
is not particularly limited, and should be adjusted appropriately
depending on the coating method or the like, and is generally 40
mass % to 99.5 mass %.
[0030] Oil stains attached to the surfaces of articles are fixed to
the surfaces of the articles by air oxidation, photoreaction, and
the like, as time passes, sometimes resulting in difficulty in
removing oil stains by wiping or washing with water. Thus, by
including an antioxidant in the coating film, it is possible to
prevent oil stains from adhering to the surfaces of articles.
[0031] The term "antioxidant" herein means a component that
prevents oil stains from transforming through oxidation caused by
heat or light in the presence of oxygen, and includes a radical
scavenger that scavenges radicals occurring in the process of the
deterioration of the oil stains, a peroxide decomposer that
decomposes peroxides produced in oil stains, thereby stabilizing
the oil stains, and an ultraviolet absorber that inhibits the
photoreaction inducing the oxidation reaction.
[0032] Any method of including an antioxidant in the coating film
can be used without any particular limitation. For example, the
antioxidant can be blended into coating composition, or once the
porous film has been formed the antioxidant can be used to fill the
voids of the porous film.
[0033] The antioxidant is not particularly limited and examples
thereof include: hydroquinone; 2,6-di-t-butyl-p-cresol;
dibutylhydroxytoluene (BHT); butylhydroxyanisole (BHA);
phenol-based compounds such as 2,6-di-t-butyl-4-ethylphenol,
2,2-methylene-bis-(4-methyl-6-t-butylphenol), n-octadecyl
3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane, and
tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate; sulfur-based
compounds such as dilauryl thiodipropionate; phosphorus-based
compounds such as triphenyl phosphite; amine-based compounds such
as phenothiazine; ascorbic acid; ascorbic acid salts; ascorbic acid
stearate; erythorbic acid; erythorbic acid salts; propyl gallate;
and tocopherol. These may be used on their own, or as a mixture
thereof.
[0034] When the antioxidant is blended in the coating composition,
the content thereof is not particularly limited. The content is
preferably 0.05 part by mass 30 parts by mass, more preferably 0.5
part by mass to 15 parts by mass with respect to 100 parts by mass
of the inorganic fine particles. When the content of the
antioxidant is less than 0.05 part by mass, effects provided by
including the antioxidant are not sufficiently exerted in some
cases. On the other hand, when the content of the antioxidant is
more than 30 parts by mass, the strength of the resultant coating
film becomes too low in some cases. Note that because the
antioxidant is a nonvolatile component, the content of the
antioxidant in the coating composition described above is identical
to the content of the antioxidant in the coating film.
[0035] Further, the coating composition can include, in addition to
the above-mentioned components, other components necessary for
imparting desired characteristics. The type of other components is
not particularly limited and it is possible to use various types of
components that can be generally blended into a coating
composition. Examples of the other components include a surfactant
with the purpose of improving coatability, an antibacterial agent
and an antimold agent with the purpose of inhibiting the occurrence
of bacteria and mold at the time of storing the coating
composition, an organic viscosity adjuster such as a water-soluble
polymer and an inorganic viscosity adjuster such as montmorillonite
both aimed at adjusting the viscosity of the composition, an
organic solvent aimed at adjusting the stability, coatability, and
drying characteristics of a coating composition suitably, and a
pigment aimed at coloring the coating film.
[0036] The content of the other components in the coating
composition varies according to the type of the other components,
and hence their content needs to be appropriately selected
depending on the other components that are used. In general, the
content of the other components in the coating composition is
preferably 10 parts by mass or less, more preferably 5 parts by
mass or less with respect to 100 parts by mass of the inorganic
fine particles. When the content of the other components is more
than 10 parts by mass, the strength of the resultant coating film
becomes too low in some cases.
[0037] Further, any method of blending the other components can be
used without any particular limitation, and the other components
can be blended according to any known method. Specifically, the
other components should be blended into the coating composition and
mixed.
[0038] Any method of applying a coating composition onto a material
to be coated can be adopted without any particular limitation, and
the coating composition can be applied by using, for example, a
dipping method, a brush, or any of various coaters. Alternatively,
the coating composition can also be applied onto a material to be
coated by pouring. By using any of these methods, the coating
composition can be applied onto a material to be coated without
producing any defects.
[0039] When the coating composition is applied onto a material to
be coated in order to obtain a porous film having less unevenness,
after the coating composition has been applied to the material to
be coated, the excess coating composition can be removed by blowing
in an air current. Further, when the coating composition is applied
onto a material to be coated by a dipping method, the unevenness of
the resultant porous film caused by the flow-down of the coating
composition can be prevented by slowly drawing up the material to
be coated. Furthermore, when the coating composition is applied
onto a material to be coated by the dipping method, it may be
possible to apply the coating composition onto the material to be
coated, and then, for example, to rotate the material to be coated,
thereby removing the excess coating composition by spinning it
out.
[0040] On the other hand, when it is difficult to perform
application or the like by using a dipping method, a brush, or any
of the various coaters, it can be preferable to perform coating by
spraying. When the coating method of spraying is performed, as
minute unevenness is formed on the resultant porous film, it is
possible to prevent the occurrence of discoloration caused by a
thin porous film.
[0041] However, when it is necessary to more reliably avoid the
blur (fluctuation) of the porous film, or to make the thickness of
the porous film larger, the above-mentioned coating method may be
performed repeatedly. Further, in order to improve the adhesion of
the coating composition to the material to be coated and to
decrease the amounts of a surfactant and the like blended, it may
be possible to perform pretreatment such as UV treatment, corona
treatment, flame treatment, or chromic acid treatment on the
material to be coated before the coating composition is applied
onto the material to be coated.
[0042] A method of drying the coating composition applied onto a
material to be coated can be appropriately selected according to
the kind of inorganic fine particles and the like. For example, the
coating composition can be dried at room temperature or dried by
heating.
[0043] In general, when the inorganic fine particles can be
solidified at room temperature, the coating composition can be
dried at room temperature. In contrast, when the inorganic fine
particles are difficult to solidify at room temperature, the
coating composition needs to be dried by heating. Further, even if
the inorganic fine particles are solidified at room temperature,
when drying is performed at room temperature (when heating is not
performed), it may take a certain period of time for the inorganic
fine particles to solidify, and hence the coating composition may
be dried by heating from the viewpoint of shortening the time that
it takes to form the resultant porous film.
[0044] When the coating composition is dried by heating, the
heating temperature is preferably 40.degree. C. to 250.degree. C.,
more preferably 45.degree. C. to 200.degree. C. When the heating
temperature is less than 40.degree. C., the inorganic fine
particles do not become solidified satisfactorily in some cases. On
the other hand, when the heating temperature is more than
250.degree. C., properties of the fluororesin particles may change.
Further, the heating time is preferably 10 minutes or more, more
preferably 30 minutes or more. When the heating time is less than
10 minutes, the inorganic fine particles do not solidify
satisfactorily in some cases. Note that, a material having low heat
conductivity, such as a resin, a thin steel plate having a
thickness of 0.2 mm or less, or the like, is used as the material
to be coated the inorganic fine particles may be solidified by
heating for just 30 seconds or more.
[0045] The porous film formed as described above has fluororesin
particles uniformly dispersed therein and has voids.
[0046] In order for this porous film to be filled sufficiently with
the water-soluble substance, the percent of voids within the porous
film is preferably 5% to 70%, more preferably 10% to 60%. When the
percent of voids is less than 5%, the amount of the water-soluble
substance that can be filled into the porous film becomes smaller,
and consequently, attached oil stains cannot be sufficiently
removed by wiping or washing with water in some cases. On the other
hand, when the percent of voids is more than 70%, the strength of
the porous film is sometimes reduced.
[0047] Furthermore, in order for the porous film to be filled
sufficiently with a water-soluble substance, the thickness of the
porous film is preferably 0.1 .mu.m to 250 .mu.m. When the
thickness is less than 0.1 .mu.m, the amount of the water-soluble
substance that can be filled into the porous film becomes smaller,
and consequently, attached oil stains cannot be sufficiently
removed by wiping or washing with water in some cases. On the other
hand, when the thickness is more than 250 .mu.m, the porous film is
too thick, sometimes resulting in the detachment of the porous film
from a material to be coated.
[0048] The water-soluble substance is used for filling the voids of
the porous film.
[0049] Here, when a coating film is formed by using a coating
composition containing a water-soluble substance, sufficient
strength is not provided by the film. In contrast, according to the
coating method of the present invention, a porous film with
excellent strength is formed, and following this a water-soluble
substance is applied to the porous film, thus the water-soluble
substance can be used to fill the voids of the porous film while
the sufficient film strength is maintained.
[0050] The water-soluble substance is a water-soluble polymer or a
water-soluble surfactant which has the characteristics of not
dissolving in oil stains and not having deliquescent properties.
They can be used individually or in combination. A substance which
dissolves in oil stains is not preferred, because, after oil stains
have attached to it, the oil stain will diffuse inside it. Further,
a substance having deliquescent property is not preferred, because,
when a coated article on which a coating film has been formed is in
use, the substance may form an aqueous solution, resulting in the
substance running away.
[0051] Further, the water-soluble substance preferably has a
characteristic of low crystallization properties. This is because
it is difficult to uniformly fill the voids of the porous film with
a substance having high crystallization properties. However, even
if a substance having high crystallization property is used, as is
it sometimes difficult for substances to crystallize in the voids
of a porous film, in these cases substances having high
crystallization properties may also be used.
[0052] The water-soluble substance has a hydrophilic group and has
a boiling point of or a decomposition point of preferably
150.degree. C. or more, more preferably 200.degree. C. or more.
When the boiling point or the decomposition point of the
water-soluble substance is less than 150.degree. C., the
water-soluble substance disappears or deteriorates through
evaporation or decomposition, and attached oil stains sometimes
cannot be removed sufficiently by wiping or washing with water,
though this occurrence may depend on the environment of use.
[0053] The water-soluble substance fills the voids of the porous
film, and partially covers the surface of the porous film. When oil
stains are attached to the surface of the porous film, the
water-soluble substance filling the voids of the porous film has
the effect of inhibiting the oil stains entrance into the inside of
the porous film. Further, the water-soluble substance covering the
surface of the porous film has the effect of preventing the oil
stains from binding to the surface of the porous film. Further,
because the water-soluble substance has hydrophilicity, the
water-soluble substance also has the effect of inhibiting the
attachment per se of oil stains caused by oil mist. Further, these
effects act in a synergistic manner, and consequently, the effect
of inhibiting the attachment of oil stains is maintained over a
long period, and even if oil stains are attached, the oil stains
can be easily removed by wiping or washing with water.
[0054] When oil stains are removed by wiping, part of the
water-soluble substance is also removed with the oil stains.
However, the amount of the water-soluble substance removed by the
wiping is very small, and hence the above-mentioned effects are
sustainable. Likewise, when oil stains are removed by washing with
water, part of the water-soluble substance is dissolved in water
and removed. However, as water-soluble substance fills the voids of
the porous film, the flow-out rate of the water-soluble substance
is very slow. Thus, even after several times of washing with water,
the above-mentioned effects are sustainable.
[0055] When a water-soluble polymer is used as the water-soluble
substance, the water-soluble polymer swells and slowly diffuses at
the time of washing with water, and as a result, dissolves in
water. Thus, the water-soluble polymer has the effect of detaching
oil stains by floating them up, the effect of inhibiting the
reattachment of detached oil stains, and has an excellent ability
to remove oil stains by washing with water. Further, when the
water-soluble polymer is filled into the voids of a porous film,
the chance that the coating of the water-soluble polymer on the
surface of the porous film is incomplete due to crystallization or
the like is very small, so the water-soluble polymer can be
effectively coated on the surface of the porous film and can be
effectively fill the voids of the porous film.
[0056] Examples of a water-soluble polymer having such
characteristics as described above include polyvinyl alcohol,
polyvinyl pyrrolidone, polyethylene glycol, polyvinyl acetate,
polyacrylic acid and a salt thereof, polyacrylamide and a copolymer
thereof, and a mixture of those polymers. In particular, the
water-soluble polymer preferably has an average polymerization
degree of 50 or more from the viewpoint of washing property. When
the average polymerization degree of the water-soluble polymer is
less than 50, its properties as a polymer are not sufficiently
exerted, and consequently, good cleaning properties are difficult
to provide in some cases.
[0057] Further, when the water-soluble polymer is used as the
water-soluble substance, a cross-linking agent may be used with the
water-soluble polymer. By using the cross-linking agent with the
water-soluble polymer, the water solubility of the water-soluble
polymer lowers, and the flow-out rate of the water-soluble polymer
at the time of washing with water can be inhibited. As a result,
even if washing with water is carried out multiple times, the
effect of inhibiting the attachment of oil stains and the effect of
removing oil stains are not easily deduced.
[0058] Any cross-linking agent can be used without any particular
limitation, and a cross-linking agent can be selected depending on
the kind of a water-soluble polymer that is used. Examples of the
cross-linking agent include: polyvalent metal compounds such as
zirconium carbonate and aluminum sulfate; adipic acid dihydrazide;
glyoxal and a reaction product thereof; and a compound having a
cross-linkable functional group such as an oxazoline group, a
carbodiimide group, an isocyanate group, or an aziridine group.
[0059] When the cross-linking agent is used, the amount of the
cross-linking agent blended is preferably 5 parts by mass or less
with respect to 100 parts by mass of the water-soluble polymer.
When the amount of the cross-linking agent blended is more than 5
parts by mass, the cross-linking reaction between the water-soluble
polymer and the cross-linking agent progresses too far. As a
result, the water-soluble polymer does not easily dissolve in water
at the time of washing with water, and consequently, the effect of
inhibiting the attachment of oil stains and the effect of removing
oil stains may be sometimes reduced.
[0060] Further, in general, when a water-soluble substance has a
lower molecular weight, the water-soluble substance diffuses in
water faster. Thus, while the water-soluble substance contacts with
cleaning water, floating oil stains up, the amount of the
water-soluble substance diffusing in the cleaning water becomes
larger. In particular, when a thinner coating film is formed, a
water-soluble substance having a lower molecular weight sometimes
does not provide the effect of improving the washing properties of
the film.
[0061] However, if the water-soluble substance having a lower
molecular weight is a water-soluble surfactant, good washing
properties are provided. This is because the water-soluble
surfactant has the effect of removing oil and inhibiting the
reattachment of the removed oil by adsorbing onto its surface.
Further, the water-soluble surfactant has the effect of making the
surface tension of water less, and hence water removal at the time
of washing with water improves, resulting in the inhibition of
excessive flow-out of the water-soluble substance caused by its
contact with water for a long time. Furthermore, the water-soluble
surfactant resists crystallization and is able to fill the voids of
the porous film well.
[0062] Examples of the water-soluble surfactant include: anionic
surfactants such as a fatty acid sodium, a monoalkyl sulfate salt,
an alkyl polyoxyethylene sulfate salt, an alkylbenzenesulfonic acid
salt, and a monoalkyl phosphate salt; cationic surfactants such as
an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, and
an alkylbenzyldimethylammonium salt; amphoteric surfactants such as
an alkyldimethylamine oxide and an alkylcarboxybetaine; and
nonionic surfactants such as a polyoxyethylene alkyl ether, a
polyoxyethylene-polyoxypropylene graft polymer, a fatty acid
sorbitan ester, an alkyl polyglucoside, a fatty acid
diethanolamide, and an alkyl monoglyceryl ether.
[0063] Note that, if the HLB value of the surfactant can be
defined, the HLB value of the surfactant is preferably 6 or more,
more preferably 8 or more. When the HLB value of the surfactant is
less than 6, the surfactant has low hydrophilicity (low water
solubility), and hence, when oil stains are attached, the
surfactant, for example, dissolves in oil, sometimes resulting in
it being unable to provide good washing properties.
[0064] For the method of applying the coating composition to a
material to be coated, any method of applying a water-soluble
substance onto a porous film can be adopted without any particular
limitation, and the water-soluble substance can be applied by
using, for example, a spraying method, a dipping method, a brush,
or any of the various coaters.
[0065] Specifically, it is recommended that a solution be prepared
by dissolving the water-soluble substance in a solvent such as
water or an alcohol, and then, this solution be applied onto the
porous film, or the porous film be immersed in this solution. On
the other hand, when the water-soluble substance is in the form of
a liquid or a paste, it is recommended that the water-soluble
substance be directly applied to the porous film, or the porous
film be directly immersed in the water-soluble substance. In
addition, when the water-soluble substance is applied onto a porous
film formed on a portion upon which it is difficult to perform the
application of the water-soluble substance on, such as a portion
with a complicated shape, a wall surface, or a ceiling surface, it
may be possible to adjust the fluidity of an application solution
by adding bubbles or particles.
[0066] Further, when the coating film formed by using the coating
method of the present invention is subjected to wiping or washing
with water many times in order to remove oil stains, some of the
water-soluble substance in the coating film runs away, sometimes
resulting in the reduction of the effect of removing oil stains and
the effect of preventing the attachment of oil stains. In this
case, it is possible to regenerate the coating film by filling the
voids of the coating film with a water-soluble substance in the
same manner as that in the above-mentioned method. It is possible
to apply the water-soluble substance to the coating film in a wet
state after the coating film has been wiped or washed with water.
However, when a water-soluble surfactant having relatively low
hydrophilicity or a water-soluble polymer having a very large
molecular weight is applied, it is better to dry a coating film and
then apply the water-soluble substance, because the water-soluble
substance is more easily able to fill the voids of the coating film
when it is dry. Further, by including the water-soluble substance
in the cleaning water itself, it is possible to carry out, the
removal of oil stains from the coating film and the application of
the water-soluble substance onto the coating film at the same
time.
[0067] Further, a method of drying the water-soluble substance
applied to the coating film should be appropriately selected
according to the kind of water-soluble substance and the like. For
example, the water-soluble substance may be dried at room
temperature or dried by heating if necessary.
[0068] The amount of the water-soluble substance filling the
coating film is preferably 5 parts by mass to 250 parts by mass,
more preferably 20 parts by mass to 200 parts by mass with respect
to 100 parts by mass of the inorganic fine particles, from the
viewpoint of ensuring oil stain washing properties. When the amount
of the water-soluble substance filled is less than 5 parts by mass,
the effect of removing oil stains sometimes is not sufficiently
provided. On the other hand, when the amount of the water-soluble
substance filled is more than the amount that is sufficient for
fully filling the voids of the coating film, a large amount of the
water-soluble substance is present on the surface of the coating
film, and the whole surface of the coating film may be covered with
the water-soluble substance. Even if such a state occurs, there are
no problems with the oil stain washing properties, but when the
content of the water-soluble substance is more than 250 parts by
mass, the film of the water-soluble substance formed on the surface
of the coating film may be detached or the article may become
unsightly.
[0069] Further, the amount of the water-soluble substance filling
the coating film is preferably 5 parts by mass to 120 parts by
mass, more preferably 20 parts by mass to 100 parts by mass with
respect to 100 parts by mass of the inorganic fine particles, for
the purpose of ensuring the oil stain washing properties and oil
stain dirt prevention properties. When the amount of the
water-soluble substance filled is less than 5 parts by mass, the
effect of removing oil stains is sometimes not sufficiently
provided. On the other hand, when the amount of the water-soluble
substance filled is more than 120 parts by mass, the fluororesin
particles and the like are covered with the water-soluble
substance, and hence the desired dirt prevention properties are
sometimes not provided.
[0070] When the water-soluble substance is applied onto a porous
film, an antioxidant can be applied with the water-soluble
substance from the viewpoint of preventing oil stains from being
fixed to the surface of an article, as described above. In
particular, in the case where the antioxidant is water-soluble, a
mixture of the water-soluble substance and the antioxidant can be
applied onto the porous film, and hence the number of steps
required in the coating method can be reduced compared with the
case where those substances are separately applied onto a porous
film. Note that, when both the substances are applied separately,
the antioxidant should be dissolved in a solvent and the resultant
solution should be applied onto the porous film.
[0071] Any method of drying the water-soluble substance or the like
applied onto a porous film may be adopted without any particular
limitation. The water-soluble substance or the like may be dried by
leaving it to stand at room temperature. Alternatively, it is also
possible to perform drying by heating if necessary.
[0072] The coating film formed by the above-mentioned coating
method comprises a porous film formed of inorganic fine particles
and having voids, with fluororesin particles dispersed in the
porous film, and a predetermined water-soluble substance (and any
antioxidant) filling the voids of the porous film. This coating
film mainly comprises the porous film formed of inorganic fine
particles and the water-soluble substance filling the voids of the
porous film, hence the whole film is hydrophilic and resists the
attachment of oil. Further, although the porous film has voids, as
the voids are filled with the water-soluble substance, oil stains
can be prevented from entering the voids, and thus removing oil
stains by wiping or washing with water is not difficult. In
addition, the water-soluble substance dissolves in water at the
time of washing with water, thereby promoting the removal of
attached oil stains. In particular, even in the case where the
amount of the water-soluble substance filling the voids is small
and oil stains are present in the voids, the oil stains can be
removed from the voids by virtue of the expansion in volume of the
water-soluble substance that takes place when the water-soluble
substance dissolves in water.
Embodiment 2
[0073] A coated article of the present invention has a coating film
formed by the above-mentioned coating method. That is, the coated
article of the present invention has a coating film which includes
a porous film formed of inorganic fine particles and having voids,
with fluororesin particles dispersed in the porous film, and a
predetermined water-soluble substance filling the voids of the
porous film.
[0074] This coating film can be formed on any article without any
particular limitation and can be used on articles in a wide range
of applications. Examples of the articles include kitchen equipment
(such as range hoods and gas ranges), air conditioners, and plant
facilities, in all of which the attachment of oil stains is
recognized as a problem.
EXAMPLES
[0075] The details of the present invention are hereinafter
described with reference to examples, but the present invention is
not restricted to the examples.
Example 1
[0076] A coating composition was prepared by adding colloidal
silica containing silica fine particles (inorganic fine particles)
having an average particle diameter of 85 nm, colloidal silica
containing silica fine particles (inorganic fine particles) having
an average particle diameter of 5 nm, and PTFE particles
(fluororesin particles) having an average particle diameter of 0.3
.mu.m to deionized water, followed by mixing, and further adding
polyoxyethylene lauryl ether (a surfactant) to the mixture,
followed by mixing. Here, in the coating composition, the content
of the silica fine particles having an average particle diameter of
85 nm was controlled to 4 mass %, the content of the silica fine
particles having an average particle diameter of 5 nm was
controlled to 1 mass %, and the content of the surfactant was
controlled to 0.05 mass %. Further, the content of the PTFE
particles was controlled to 6 to 7 parts by mass with respect 100
parts by mass of the total silica fine particles.
[0077] A stainless-steel plate was immersed in the resultant
coating composition, this was slowly drawn up, and dried at
100.degree. C. for 30 minutes, thereby forming a porous film (film
thickness: 0.8 .mu.m). The stainless-steel plate on which the
porous film was formed was immersed in an aqueous solution
containing 2 mass % polyvinyl pyrrolidone. Next, the
stainless-steel plate was drawn up from the aqueous solution, and
excess aqueous solution was shaken off, followed by drying at room
temperature, in order to form a coating film filled with polyvinyl
pyrrolidone. Here, the content of polyvinyl pyrrolidone of the
coating film was controlled to 30 parts by mass with respect to 100
parts by mass of the silica fine particles.
Examples 2 to 4
[0078] A stainless-steel plate on which a coating film was formed
was prepared in each of Examples 2 to 4 in the same manner as that
in Example 1, except that the thickness of the porous film was
changed and the kind and type of water-soluble substance filling
the voids of the porous film was changed. The thickness of the
porous film was adjusted by, for example, increasing or decreasing
the number of applications of the coating composition onto the
stainless-steel plate.
[0079] In Example 2, polyethylene glycol (polymerization degree:
4,000) was used as the water-soluble substance, and a
stainless-steel plate on which a porous film (film thickness: 1.0
.mu.m) was formed was immersed in an aqueous solution containing 2
mass % polyethylene glycol, followed by drying at room temperature,
in order to form a coating film. The content of polyethylene glycol
in the coating film was controlled to 45 parts by mass with respect
to 100 parts by mass of the silica fine particles.
[0080] In Example 3, sodium lauryl sulfate was used as the
water-soluble substance, and a stainless-steel plate on which a
porous film (film thickness: 0.5 .mu.m) was formed was immersed in
an aqueous solution containing 2 mass % sodium lauryl sulfate,
followed by drying at room temperature, in order to form a coating
film. The content of sodium lauryl sulfate in the coating film was
controlled to 32 parts by mass with respect to 100 parts by mass of
the silica fine particles.
[0081] In Example 4, a polyoxyethylene-polyoxypropylene block
polymer (ADEKA Pluronic L-64, ADEKA CORPORATION) was used as the
water-soluble substance, and a stainless-steel plate on which a
porous film (film thickness: 0.8 .mu.m) was formed was immersed in
an aqueous solution containing a 2 mass %
polyoxyethylene-polyoxypropylene block polymer, followed by drying
at room temperature, in order to form a coating film. The content
of the polyoxyethylene-polyoxypropylene block polymer in the
coating film was controlled to 35 parts by mass with respect to 100
parts by mass of the silica fine particles.
Example 5
[0082] A coating composition was prepared by adding an alumina
powder (inorganic fine particles) having an average particle
diameter of 0.5 .mu.m, Ethyl silicate 48 (inorganic fine particles,
Colcoat Co., Ltd.), PTFE particles (fluororesin particles) having
an average particle diameter of 0.3 .mu.m, phosphoric acid, and
polyethylene glycol lauryl ether (a surfactant) to deionized water,
followed by mixing. Here, in the coating composition, the content
of the alumina particles having an average particle diameter of 0.5
um was controlled to 5 mass %, the content of Ethyl silicate 48 was
controlled to 1 mass %, the content of phosphoric acid was
controlled to 0.2 mass %, and the content of the surfactant was
controlled to 0.05 mass %. Further the content of the PTFE
particles was controlled to 7 parts by mass with respect 100 parts
by mass of the total inorganic fine particles.
[0083] The resultant coating composition was applied onto a
stainless-steel plate by spray coating, and was dried at
150.degree. C. for 30 minutes, thereby forming a porous film (film
thickness: 2.1 .mu.m). The stainless-steel plate on which the
porous film was formed was immersed in an aqueous solution
containing 2 mass % polyvinyl pyrrolidone. Next, the
stainless-steel plate was drawn up from the aqueous solution, and
excess aqueous solution was shaken off, followed by drying at room
temperature, in order to form a coating film filled with polyvinyl
pyrrolidone. Here, the content of polyvinyl pyrrolidone in the
coating film was controlled to 50 parts by mass with respect to 100
parts by mass of the inorganic fine particles.
Examples 6 and 7
[0084] A stainless-steel plate on which a coating film was formed
was prepared in each of Examples 6 and 7 in the same manner as that
in Example 5, except that the thickness of the porous film was
changed and the kind and type of the water-soluble substance
filling the voids of the porous film were changed. The thickness of
the porous film was adjusted by, for example, increasing or
decreasing the number of applications of the coating composition
onto the stainless-steel plate.
[0085] In Example 6, sorbitan lauryl ester (ADEKA TOL S-20, ADEKA
CORPORATION) was used as the water-soluble substance, and a
stainless-steel plate on which a porous film (film thickness: 3.0
.mu.m) was formed was immersed in an aqueous solution containing 2
mass % sorbitan lauryl ester, followed by drying at room
temperature, in order to form a coating film. The content of
sorbitan lauryl ester in the coating film was controlled to 62
parts by mass with respect to 100 parts by mass of the inorganic
fine particles.
[0086] In Example 7, a polyoxyethylene-polyoxypropylene block
polymer (ADEKA Pluronic L-64, ADEKA CORPORATION) was used as the
water-soluble substance, and a stainless-steel plate on which a
porous film (film thickness: 3.2 .mu.m) was formed was immersed in
an aqueous solution containing a 2 mass %
polyoxyethylene-polyoxypropylene block polymer, followed by drying
at room temperature, in order to form a coating film. The content
of the polyoxyethylene-polyoxypropylene block polymer in the
coating film was controlled to 58 parts by mass with respect to 100
parts by mass of the inorganic fine particles.
Comparative Example 1
[0087] In Comparative Example 1, only a coating film of inorganic
fine particles was formed, and no water-soluble substance was
filled.
[0088] A coating composition was prepared by adding colloidal
silica containing silica fine particles (inorganic fine particles)
having an average particle diameter of 85 nm and colloidal silica
containing silica fine particles (inorganic fine particles) having
an average particle diameter of 5 nm to deionized water, followed
by mixing, and further adding polyoxyethylene lauryl ether (a
surfactant) to the mixture, followed by mixing. Here, in the
coating composition, the content of the silica fine particles
having an average particle diameter of 85 nm was controlled to 4
mass %, the content of the silica fine particles having an average
particle diameter of 5 nm was controlled to 1 mass %, and the
content of the surfactant was controlled to 0.05 mass %.
[0089] A stainless-steel plate was immersed in the resultant
coating composition, this was slowly drawn up, and dried at
100.degree. C. for 30 minutes, in order to form a coating film
(film thickness: 1.0 .mu.m).
Comparative Example 2
[0090] In Comparative Example 2, a coating film only formed of
inorganic fine particles was filled with a water-soluble
substance.
[0091] A stainless-steel plate on which a porous film (film
thickness: 0.5 .mu.m) was formed according to the same procedure as
that in Comparative Example 1 this was immersed in an aqueous
solution containing 2 mass % polyvinyl pyrrolidone. Next, the
stainless-steel plate was drawn up from the aqueous solution, and
the excess aqueous solution was shaken off, followed by drying at
room temperature, in order to form a coating film filled with
polyvinyl pyrrolidone. Here, the content of polyvinyl pyrrolidone
of the coating film was controlled to 30 parts by mass with respect
to 100 parts by mass of the silica fine particles.
Comparative Example 3
[0092] In Comparative Example 3, a coating film which was formed of
inorganic fine particles and fluororesin particles to which no
water-soluble substance was filled.
[0093] A coating composition was prepared by adding colloidal
silica containing silica fine particles (inorganic fine particles)
having an average particle diameter of 85 nm, colloidal silica
containing silica fine particles (inorganic fine particles) having
an average particle diameter of 5 nm, and PTFE particles
(fluororesin particles) having an average particle diameter of 0.3
.mu.m to deionized water, followed by mixing, and further adding
polyoxyethylene lauryl ether (a surfactant) to the mixture,
followed by mixing. Here, in the coating composition, the content
of the silica fine particles having an average particle diameter of
85 nm was controlled to 4 mass %, the content of the silica fine
particles having an average particle diameter of 5 nm was
controlled to 1 mass %, and the content of the surfactant was
controlled to 0.05 mass %. Further, the content of the PTFE
particles was controlled to 9 parts by mass with respect 100 parts
by mass of the total silica fine particles.
[0094] A stainless-steel plate was immersed in the resultant
coating composition, slowly drawn up, and dried at 100.degree. C.
for 30 minutes, in order to form a coating film (film thickness:
0.8 .mu.m).
[0095] Each of the stainless-steel plates prepared in Examples 1 to
7 and Comparative Examples 1 to 3 were exposed for 5 minutes to oil
smoke produced by heating vegetable oil on a hot plate, to produce
oil stains. Then, the attached oil stains were dissolved with
hexane, and the resultant solution was collected and subjected to
liquid chromatography to perform quantitative determination. Next,
each of the stainless-steel plates which were prepared in the same
manner as described above and to which oil stains were attached
were washed by being immersed in water at 40.degree. C. for 30
seconds. After that, in the same manner as described above, the
remaining oil stains were dissolved with hexane, and the resultant
solution was collected and subjected to liquid chromatography to
perform quantitative determination. Table 1 shows the results.
TABLE-US-00001 TABLE 1 Amount of attached oil (mg/dm.sup.2)
Fluororesin Water-soluble Before washing After washing Inorganic
fine particles particles substance with water with water Example 1
Silica fine particles PTFE Polyvinyl pyrrolidone 25 6 Example 2
Silica fine particles PTFE Polyethylene glycol 34 5 Example 3
Silica fine particles PTFE Sodium lauryl sulfate 38 2 Example 4
Silica fine particles PTFE Polyoxyethylene- 19 2 polyoxypropylene
block polymer Example 5 Alumina powder PTFE Polyvinyl pyrrolidone
78 7 Ethyl silicate 48 Example 6 Alumina powder PTFE Sorbitan
lauryl ester 85 8 Ethyl silicate 48 Example 7 Alumina powder PTFE
Polyoxyethylene- 69 4 Ethyl silicate 48 polyoxypropylene block
polymer Comparative Silica fine particles -- -- 120 105 Example 1
Comparative Silica fine particles -- Polyvinyl pyrrolidone 135 62
Example 2 Comparative Silica fine particles PTFE -- 15 10 Example
3
[0096] As shown in Table 1, the results of each of the
stainless-steel plates prepared in Examples 1 to 7 show that the
amount of attached oil stains was small and the attached oil stains
were easily removed by washing with water. In contrast, the results
of the stainless-steel plate prepared in Comparative Example 1 (a
coating film containing no fluororesin particle and no
water-soluble substance) showed that the amount of attached oil
stains was large and the attached oil stains were not sufficiently
removed by washing with water. Further, the results of the
stainless-steel plate prepared in Comparative Example 2 (a coating
film containing no fluororesin particle) showed that the amount of
attached oil stains was large, but the amount of the attached oil
stains removed by washing with water was larger. The results of the
stainless-steel plate prepared in Comparative Example 3 (a coating
film containing no water-soluble substance) showed that, though the
amount of attached oil stains was small, the amount of the attached
oil stains removed by washing with water was small. Therefore, it
is possible to conclude that, when a coating film contains no
fluororesin particles, the effect of preventing the attachment of
oil stains is not sufficiently provided, and when a coating film
contains no water-soluble substance, the effect of removing oil
stains is not sufficiently provided.
Example 8
[0097] A stainless-steel plate on which the same porous film as
that prepared in Example 4 was formed was immersed in an aqueous
solution containing 2 mass % polyvinyl pyrrolidone and 0.1 mass %
dibutylhydroxytoluene (an antioxidant). Next, the stainless-steel
plate was drawn up from the aqueous solution, and the excess
aqueous solution was shaken off, followed by drying at room
temperature, in order to form a coating film filled with polyvinyl
pyrrolidone and dibutylhydroxytoluene. Here, in the coating film,
the content of polyvinyl pyrrolidone was controlled to 30 parts by
mass with respect to 100 parts by mass of the silica fine
particles, and the content of dibutylhydroxytoluene was controlled
to 1.5 parts by mass with respect to 100 parts by mass of the
silica fine particles.
Examples 9 to 11
[0098] A stainless-steel plate on which a coating film was formed
was prepared in each of Examples 9 to 11 in the same manner as that
in Example 8, except that the kind and type of antioxidant were
changed.
[0099] In Example 9, tocopherol was used as the antioxidant, and a
stainless-steel plate on which a porous film was formed was
immersed in an aqueous solution containing 2 mass % polyvinyl
pyrrolidone and 0.2 mass % tocopherol, followed by drying at room
temperature, in order to form a coating film. Here, in the coating
film, the content of polyvinyl pyrrolidone was controlled to 30
parts by mass with respect to 100 parts by mass of the silica fine
particles, and the content of tocopherol was controlled to 3 parts
by mass with respect to 100 parts by mass of the silica fine
particles.
[0100] In Example 10, hydroquinone was used as the antioxidant, and
a stainless-steel plate on which a porous film was formed was
immersed in an aqueous solution containing 2 mass % polyvinyl
pyrrolidone and 1 mass % hydroquinone, followed by drying at room
temperature, in order to form a coating film. Here, in the coating
film, the content of polyvinyl pyrrolidone was controlled to 30
parts by mass with respect to 100 parts by mass of the silica fine
particles, and the content of hydroquinone was controlled to 15
parts by mass with respect to 100 parts by mass of the silica fine
particles.
[0101] In Example 11, sodium erythorbate was used as the
antioxidant, and a stainless-steel plate on which a porous film was
formed was immersed in an aqueous solution containing 2 mass %
polyvinyl pyrrolidone and 2 mass % sodium erythorbate, followed by
drying at room temperature, in order to form a coating film. Here,
in the coating film, the content of polyvinyl pyrrolidone was
controlled to 20 parts by mass with respect to 100 parts by mass of
the silica fine particles, and the content of sodium erythorbate
was controlled to 20 parts by mass with respect to 100 parts by
mass of the silica fine particles.
[0102] Each of the stainless-steel plates prepared in Examples 4
and 8 to 11 was installed in an exhaust air duct in a kitchen and
was kept there for half a year. Each stainless-steel plate was
taken off from the exhaust air duct and washed with tap water.
After that, the remaining oil stains were dissolved with hexane,
and the resultant solution was collected and subjected to liquid
chromatography to perform quantitative determination. Note that, in
the case of each of the stainless-steel plates with a coating film
prepared in Examples 4 and 11, the amount of oil stains before
washing with tap water was also determined by liquid
chromatography. Table 2 shows the results.
TABLE-US-00002 TABLE 2 Amount of attached oil (mg/dm.sup.2) Before
washing After washing Antioxidant with water with water Example 4
-- 240 93 Example 8 Dibutylhydroxytoluene -- 12 Example 9
Tocopherol -- 9 Example 10 Hydroquinone 205 27 Example 11 Sodium
erythorbate -- 39
[0103] As shown in Table 2, the results of the stainless-steel
plate prepared in Example 4 showed that, after half a year passed,
attached oil stains were difficult to remove by washing with water,
but each of the stainless-steel plates prepared in Examples 8 to 11
showed that, even after half a year passed, attached oil stains
were easily removed by washing with water. Therefore, it is
possible to conclude that a coating film containing an antioxidant
leads to the prevention of oxidation, etc., of oil stains, and even
after a long period has passed, attached oil stains are easily
removed by washing with water.
Example 12
[0104] A coating composition was prepared by adding colloidal
silica containing silica fine particles (inorganic fine particles)
having an average particle diameter of 85 nm, colloidal silica
containing silica fine particles (inorganic fine particles) having
an average particle diameter of 5 nm, and PTFE particles
(fluororesin particles) having an average particle diameter of 0.3
.mu.m to deionized water, followed by mixing, and further adding
polyoxyethylene lauryl ether (a surfactant) to the mixture,
followed by mixing. Here, in the coating composition, the content
of the silica fine particles having an average particle diameter of
85 nm was controlled to 3.5 mass %, the content of the silica fine
particles having an average particle diameter of 5 nm was
controlled to 1.2 mass %, and the content of the surfactant was
controlled to 0.05 mass %. Further, the content of the PTFE
particles was controlled to 15 parts by mass with respect 100 parts
by mass of the total silica fine particles.
[0105] A stainless-steel plate was immersed in the resultant
coating composition, slowly drawn up, and dried at 100.degree. C.
for 30 minutes, in order to form a porous film (film thickness: 1.5
.mu.m). The stainless-steel plate on which the porous film was
formed was immersed in an aqueous solution containing 1 mass %
polyvinyl alcohol (GOHSEFIMER Z-200 manufactured by The Nippon
Synthetic Chemical Industry Co., Ltd.). Next, the stainless-steel
plate was drawn up from the aqueous solution, and the excess
aqueous solution was shaken off, followed by drying at room
temperature, in order to form a coating film filled with polyvinyl
alcohol. Here, the content of polyvinyl alcohol in the coating film
was controlled to 35 parts by mass with respect to 100 parts by
mass of the silica fine particles.
Example 13
[0106] A stainless-steel plate on which a coating film was formed
was prepared in Example 13 in the same manner as that of Example
12, except that an aqueous solution prepared by using polyvinyl
alcohol and adipic acid dihydrazide was used. Here, the amount of
adipic acid dihydrazide blended in the aqueous solution was
controlled to 1.5 parts by mass with respect to 100 parts by mass
of polyvinyl alcohol.
Comparative Example 4
[0107] A stainless-steel plate on which a coating film was formed
was prepared in Comparative Example 4 in the same manner as that in
Example 12, except that sorbitol, which is a water-soluble
substance having a lower molecular weight, was used instead of
polyvinyl alcohol. Here, the content of sorbitol in the aqueous
solution was controlled to 5 mass %.
[0108] Each of the stainless-steel plates prepared in Examples 12
and 13 and Comparative Example 4 was exposed for 5 minutes to oil
smoke produced by heating a vegetable oil on a hot plate, to
produce oil stains. Then, the attached oil stains were dissolved
with hexane, and the resultant solution was collected and subjected
to liquid chromatography to perform quantitative determination.
Next, each of the stainless-steel plates which were prepared in the
same manner as described above and to which oil stains were
attached was washed by pouring water at about 40.degree. C. for
about 10 seconds. After that, in the same manner as described
above, the remaining oil stains were dissolved with hexane, and the
resultant solution was collected and subjected to liquid
chromatography to perform quantitative determination. The cycle
including the attachment of oil stains and the washing thereof was
repeated, that is, the second cycle, the third cycle, and the
fourth cycle were performed. The amount of attached oil after each
cycle was evaluated. Table 3 shows the results.
TABLE-US-00003 TABLE 3 Amount of attached oil (mg/dm.sup.2) After
After After After Before washing first second third fourth with
water cycle cycle cycle cycle Example 12 85 7 11 29 31 Example 13
91 8 9 19 18 Comparative 82 38 92 82 90 Example 4
[0109] As shown in Table 3, the results of each of the
stainless-steel plates prepared in Examples 12 and 13 showed that,
even after the fourth cycle, attached oil stains were easily
removed by washing with water. In particular, the results of the
stainless-steel plate prepared in Example 13 in which an aqueous
solution prepared by using adipic acid dihydrazide serving as a
cross-linking agent together with polyvinyl alcohol was used showed
that, even after the fourth cycle, the amount of attached oil
stains removed was remarkably high. In contrast, the results of the
stainless-steel plate prepared in Comparative Example 4 showed
that, as the number of the cycle increases, oil stains became more
difficult to remove.
[0110] Next, the stainless-steel plate prepared in Example 6 was
used to carry out the following experiments.
[0111] The stainless-steel plates was exposed for 5 minutes to oil
smoke produced by heating a vegetable oil on a hot plate, thereby
attaching oil stains thereto. Then, the attached oil stains were
dissolved with hexane, and the resultant solution was collected and
subjected to liquid chromatography to perform quantitative
determination. Next, the stainless-steel plate which was prepared
in the same manner as described above and to which oil stains were
attached was washed by using an aqueous solution containing 2 mass
% sorbitan lauryl ester. After that, in the same manner as
described above, the remaining attached oil stains were subjected
to liquid chromatography to perform quantitative determination.
[0112] The cycle including the attachment of oil stains and the
washing thereof described above was repeated, that is, the second
cycle, the third cycle, and the fourth cycle were performed. The
amount of attached oil after each cycle was evaluated. Table 4
shows the results.
TABLE-US-00004 TABLE 4 Amount of attached oil (mg/dm.sup.2) After
After After After Before washing first second third fourth with
water cycle cycle cycle cycle Example 6 98 8 12 20 12
[0113] As shown in Table 4, the results of the stainless-steel
plate prepared in Example 6 showed that, even after the fourth
cycle, attached oil stains were easily removed by washing with
water. Further, it was found that washing with an aqueous solution
containing the water-soluble substance replenished the
water-soluble substance in the coating film, resulting in the
effect of removing attached oil stains being maintained.
Comparative Example 5
[0114] In Comparative Example 5, a coating film which was formed of
inorganic fine particles and fluororesin particles but which was
not filled with any water-soluble substance was produced. Here, a
coating film formed of a porous film was formed on a
stainless-steel plate in the same manner as that in Example 12,
except that polyvinyl alcohol did not fill the porous film.
[0115] Next, each of the stainless-steel plates prepared in
Examples 4, 5, and 12 and Comparative Example 5 were used to carry
out the following experiment.
[0116] Each of the stainless-steel plates was exposed for 5 minutes
to oiismoke produced by heating a vegetable oil on a hot plate, to
produce oil stains. Then, the attached oil stains were dissolved
with hexane, and the resultant solution was collected and subjected
to liquid chromatography to perform quantitative determination.
Next, each of the stainless-steel plates which were prepared in the
same manner as described above and those to which oil stains were
attached were lightly wiped twice with a towel cloth impregnated
with water. After that, in the same manner as described above, the
remaining attached oil stains were subjected to liquid
chromatography to perform quantitative determination. Table 5 shows
the results.
TABLE-US-00005 TABLE 5 Amount of attached oil (mg/dm.sup.2) Before
wiping After wiping Example 4 25 12 Example 5 76 9 Example 12 92 15
Comparative 125 102 Example 5
[0117] As shown in Table 5, the results of each of the
stainless-steel plates prepared in Examples 4, 5, and 12 showed
that attached oil stains were easily removed by wiping. In
contrast, the results of the stainless-steel plate prepared in
Comparative Example 5 showed that attached oil stains were not
sufficiently removed by wiping.
[0118] As the above-mentioned results show, it is possible to form,
by adopting the coating method of the present invention, a coating
film which exhibits an excellent effect for inhibiting the
attachment of oil stains for a long period and from which, even if
oil stains are attached, the oil stains can be easily removed by
wiping or washing with water.
[0119] Note that this international application claims priority
based on Japanese Patent Application No. 2009-031673 filed on Feb.
13, 2009, the disclosure of which is incorporated herein by
reference in its entirety.
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